Biobased Resin for Sustainable Stereolithography: 3D Printed Vegetable Oil Acrylate Reinforced with Ultra-Low Content of Nanocellulose for Fossil Resin Substitution.

The use of biobased materials in additive manufacturing is a promising long-term strategy for advancing the polymer industry toward a circular economy and reducing the environmental impact. In commercial 3D printing formulations, there is still a scarcity of efficient biobased polymer resins. This research proposes vegetable oils as biobased components to formulate the stereolithography (SLA) resin. Application of nanocellulose filler, prepared from agricultural waste, remarkably improves the printed material's performance properties. The strong bonding of nanofibrillated celluloses' (NFCs') matrix helps develop a strong interface and produce a polymer nanocomposite with enhanced thermal properties and dynamical mechanical characteristics. The ultra-low NFC content of 0.1-1.0 wt% (0.07-0.71 vol%) was examined in printed samples, with the lowest concentration yielding some of the most promising results. The developed SLA resins showed good printability, and the printing accuracy was not decreased by adding NFC. At the same time, an increase in the resin viscosity with higher filler loading was observed. Resins maintained high transparency in the 500-700 nm spectral region. The glass transition temperature for the 0.71 vol% composition increased by 28°C when compared to the nonreinforced composition. The nanocomposite's stiffness has increased fivefold for the 0.71 vol% composition. The thermal stability of printed compositions was retained after cellulose incorporation, and thermal conductivity was increased by 11%. Strong interfacial interactions were observed between the cellulose and the polymer in the form of hydrogen bonding between hydroxyl and ester groups, which were confirmed by Fourier-transform infrared spectroscopy. This research demonstrates a great potential to use acrylated vegetable oils and nanocellulose fillers as a feedstock to produce high-performance resins for sustainable SLA 3D printing.

Biodegradable Poly(butylene succinate) Laminate with Nanocellulose Interphase Layer for High-Barrier Packaging Film Application.

In response to rising concerns over the environmental and human health ramifications of polymers derived from petroleum, particularly in the food packaging industry, research has pivoted towards more sustainable materials. Poly(butylene succinate) (PBS), selected as the polymer matrix, stands out as one of the most promising bio-based and biodegradable polymers suitable for film blowing and lamination. A layered spray-coating technique was employed to apply 1, 5, 10, and 20 layers of nanofibrillated cellulose (NFC) between blown PBS films, creating a three-layer laminate structure. NFC sourced from minimally processed hemp stalk waste highlights the potential for minimizing environmental impact. The water vapor transmission rate (WVTR) of these films, a critical parameter for food packaging, was assessed in a controlled environment at 38 °C and 90% relative humidity over a period of two months. The integration of a single NFC layer, constituting 0.35% of the composite's weight, was observed to significantly reduce the WVTR by up to 5.5-fold. It was noted that higher NFC layer counts above 10 reduced the adhesion within the laminate layers. Morphological assessments showed that the number of structural defects increased with a higher count of NFC layers. As the count of NFC layers increased, the optical transparency of the laminates dropped from approximately 65% to 25% in the visible light spectrum. Notably, by weight percent, NFC proved to be an effective barrier even without chemical modification. The developed laminates stand out as a viable, green option for food packaging, offering a sustainable and renewable solution.

Sustainable hemp-based bioplastics with tunable properties via reversible thermal crosslinking of cellulose.

Modern bioplastics and biocomposites frequently contain non-biodegradable or non-sustainable components and require complex recycling routes. Sustainable materials require integrating bio-based, cheap, widely available, recycled, or waste components. In order to incorporate these concepts, we selected hemp stalk waste, the industrial byproducts glycerol and xylan (hemicellulose), and citric acid as key components. Hemp stalks were processed into cast papers using only mechanical processes and no chemical modifications or pre-treatments. Cast papers were impregnated with a crosslinking mixture of glycerol, xylan, citric acid, and the plasticizer polyethylene glycol (PEG). Thermal crosslinking was performed as a single-step reaction by curing materials at 140 °C. All prepared bioplastics were washed in water for 48 h and extensively tested for water resistance and water absorption. A recycling route with depolymerization (for pulp recovery) in sodium hydroxide is demonstrated. A comprehensive analysis of crosslinking reaction is provided via FTIR and rheology, supplemented by structure analysis via SEM. A 7-fold reduction in water uptake was achieved compared to cast hemp paper. Obtained bioplastics, after washing in water, show elastic modulus up to 2.9 GPa, tensile strength up to 70 MPa, and elongation up to 4.3 %. As a result of component ratio variation, bioplastics achieve a high tuneability of properties ranging from brittle to ductile. Dielectric analysis indicates that bioplastics have the potential for application in electric insulation. A three-layer laminate is demonstrated as a concept for potential application as an adhesive for bio-based composites.

Poly(Butylene Succinate) Hybrid Multi-Walled Carbon Nanotube/Iron Oxide Nanocomposites: Electromagnetic Shielding and Thermal Properties.

To address the ever-increasing electromagnetic interference (EMI) pollution, a hybrid filler approach for novel composites was chosen, with a focus on EMI absorbance. Carbon nanofiller loading was limited to 0.6 vol.% in order to create a sustainable and affordable solution. Multiwall carbon nanotubes (MWCNT) and iron oxide (Fe3O4) nanoparticles were mixed in nine ratios from 0.1 to 0.6 vol.% and 8.0 to 12.0 vol.%, respectively. With the addition of surfactant, excellent particle dispersion was achieved (examined with SEM micrographs) in a bio-based and biodegradable poly(butylene succinate) (PBS) matrix. Hybrid design synergy was assessed for EMI shielding using dielectric spectroscopy in the microwave region and transmittance in the terahertz range. The shielding effectiveness (20-52 dB) was dominated by very high absorption at 30 GHz, while in the 0.1 to 1.0 THz range, transmittance was reduced by up to 6 orders of magnitude. Frequency-independent AC electrical conductivity (from 10-2 to 107 Hz) was reached upon adding 0.6 vol.% MWCNT and 10 vol.% Fe3O4, with a value of around 3.1 × 10-2 S/m. Electrical and thermal conductivity were mainly affected by the content of MWCNT filler. The thermal conductivity scaled with the filler content and reached the highest value of 0.309 W/(mK) at 25 °C with the loading of 0.6 vol.% MWCNT and 12 vol.% Fe3O4. The surface resistivity showed an incremental decrease with an increase in MWCNT loading and was almost unaffected by an increase in iron oxide loading. Thermal conductivity was almost independent of temperature in the measured range of 25 to 45 °C. The nanocomposites serve as biodegradable alternatives to commodity plastic-based materials and are promising in the field of electromagnetic applications, especially for EMI shielding.

Multilayered Composites with Carbon Nanotubes for Electromagnetic Shielding Application.

Bulk polylactic acid (PLA)/multiwall carbon nanotube (MWCNT) composites were prepared and investigated in wide frequency ranges (20 Hz-1 MHz and 24-40 GHz). It was determined that the percolation threshold in bulk PLA/MWCNT composites is close to 0.2 vol.% MWCNT. However, the best microwave dielectric properties and absorption were observed in composites with 3.0-5.0 vol.% MWCNT. Therefore, for future investigations, we selected layered (laminate) polymeric structures with gradual changes in MWCNT concentration from 0.2 to 8.0 vol.% MWCNT. Two approaches to laminate structure designs were examined and compared: a five-layer composite and a nine-layer composite that included four pure PLA middle layers. The addition of MWCNT enhanced the elastic modulus by up to 1.4-fold and tensile strength by up to 1.2-fold, with the best performance achieved at 5.0 vol.% loading. High microwave shielding was observed for these layered PLA/MWCNT structures with a gradient change in MWCNT concentration (up to 26 dB in both transmission and absorption coefficients) in the broad frequency range (from 24 to 40 GHz). Obtained structures are highly anisotropic, and the absorption coefficient is 2-5 dB higher in the direction of MWCNT concentration increase; however, the transmission coefficient is the same in both directions. The properties of microwave absorption are mainly unaffected by the additional polymeric layers. The absorption of the layered structure is greater than the absorption of single-layer composites with an optimal MWCNT concentration of the same thickness. The proposed laminate structure design is promising in the field of efficient electromagnetic shielding.

Comparison of Carbon-Nanoparticle-Filled Poly(Butylene Succinate-co-Adipate) Nanocomposites for Electromagnetic Applications.

Electrostatic dissipative (ESD), anti-static (AS), and electromagnetic interference (EMI) shielding materials are commonly based on commodity fossil-fuel-based plastics. This, in turn, contributes to ever-growing non-biodegradable plastic pollution. Graphene nanoplatelets (GN), multi-walled carbon nanotubes (MWCNT), nanostructured carbon black (NCB), and amorphous carbon black (CB) were utilized as nanofillers to prepare bio-based and biodegradable poly(butylene succinate-co-adipate) (PBSA) nanocomposites. Solvent-cast composites were prepared with 1.1 to 30.0 vol.% nanoparticle loading. The literature mainly focuses on relatively low loadings; therefore, for this research, filler loadings were increased up to 30 vol.% but the maximum loading for NCB and CB loadings only reached 17.4 vol.% due to a lack of dimensional stability at higher loadings. The composites were characterized using tensile testing, volumetric and surface conductivity measurements, thermal conductivity measurements, dielectric spectroscopy in the microwave region, and transmittance in the terahertz range. Tensile tests showed excellent carbon filler compatibility and enhanced tensile strength for loadings up to 5 vol.% (up to 20 vol.% for MWCNT). The highest thermal conductivity values were reached for the MWCNT filler, with the 30.0 vol.% filled composite reaching 0.756 W/mK (262% increase over PBSA). All fillers were able to produce composites that yielded volume conductivities above 10-10 S/m. Composites with MWCNT, GN, and NCB inclusions above the percolation threshold are suitable for EMI applications in the microwave and THz frequency range.

Data on FTIR, photo-DSC and dynamic DSC of triethylene glycol dimethacrylate and N-vinylpyrrolidone copolymerization in the presence of ionic liquids.

Here we show the effect of the ionic liquid nature, its content and monomer/crosslinker ratio on the copolymerization of N-vinylpyrrolidone (NVP) with triethylene glycol dimethacrylate (TEGDMA) induced by UV or heat irradiation. For the first time, kinetics curves of photopolymerization NVP with TEGDMA in the presence of ionic liquids are obtained. The ionic liquids EmimBF4, BmimBF4, OmimBF4 and EmimTFSI with different cation and anion structures and lengths of the alkyl radical were varied in photopolymer compositions. To understand the influence of ionic liquids on the polymerization kinetics, photo-DSC, dynamic DSC, and FTIR were performed. Parameters obtained from photo-DSC curves allowed to develop the methodology for the stereolithography of ionogels. The presented data constitutes the complete dataset useful for 3D-printing of ionogels with high accuracy, which is reported in the main article.

Sustainable Wax Coatings Made from Pine Needle Extraction Waste for Nanopaper Hydrophobization.

We combine renewable and waste materials to produce hydrophobic membranes in the present work. Cellulose nanopaper prepared from paper waste was used as a structural component for the membrane. The pine wax was reclaimed from pine needle extraction waste and can be regarded as a byproduct. The dip-coating and spray-coating methods were comprehensively compared. In addition, the solubility of wax in different solvents is reported, and the concentration impact on coating quality is presented as the change in the contact angle value. The sensile drop method was used for wetting measurements. Spray-coating yielded the highest contact angle with an average of 114°, while dip-coating reached an average value of 107°. Scanning electron microscopy (SEM) was used for an in-depth comparison of surface morphology. It was observed that coating methods yield significantly different microstructures on the surface of cellulose fibers. The wax is characterized by nuclear magnetic resonance (NMR) spectroscopy and differential scanning calorimetry (DSC). Pine wax has a melting temperature of around 80 °C and excellent thermal stability in oxygen, with a degradation peak above 290 °C. Fourier transform infrared spectroscopy (FTIR) was used to identify characteristic groups of components and show the changes on coated nanopaper. Overall, the results of this work yield important insight into wax-coated cellulose nanopapers and a comparison of spray- and dip-coating methods. The prepared materials have a potential application as membranes and packaging materials.

Hydrothermal Ageing Effect on Reinforcement Efficiency of Nanofibrillated Cellulose/Biobased Poly(butylene succinate) Composites.

Nanofibrillated cellulose (NFC) is a sustainable functional nanomaterial known for its high strength, stiffness, and biocompatibility. It has become a key building block for the next-generation of lightweight, advanced materials for applications such as consumer products, biomedical, energy storage, coatings, construction, and automotive. Tunable and predictable durability under environmental impact is required for high performance applications. Bio-based poly (butylene succinate) (PBS) composites containing up to 50% NFC content were designed and aged in distilled water or at high relative humidity (RH98%). PBS/NFC composites are characterized by up to 10-fold increased water absorption capacity and diffusivity and the data are correlated with model calculations. Aged samples exhibited decreased crystallinity and melting temperature. Incorporation of NFC into PBS showed up to a 2.6-fold enhancement of the elastic modulus, although accompanied by a loss of strength by 40% and 8-fold reduction in the strain at failure of maximally loaded composites. Hydrothermal ageing had almost no influence on the tensile characteristics of PBS; however, there were considerable degradation effects in PBS/NFC composites. Altered reinforcement efficiency is manifested through a 3.7-fold decreased effective elastic moduli of NFC determined by applying the Halpin-Tsai model and a proportional reduction of the storage moduli of composites. The adhesion efficiency in composites was reduced by hydrothermal ageing, as measured Puckanszky's adhesion parameter for the strength, which decreased from 3 to 0.8. For the loss factor, Kubat's adhesion parameter was increased by an order. PBS filled with 20 wt.% NFC is identified as the most efficient composition, for which negative environmental degradation effects are counterbalanced with the positive reinforcement effect. The PBS matrix can be used to protect the NFC network from water.

Lignin and Xylan as Interface Engineering Additives for Improved Environmental Durability of Sustainable Cellulose Nanopapers.

Cellulose materials and products are frequently affected by environmental factors such as light, temperature, and humidity. Simulated UV irradiation, heat, and moisture exposure were comprehensively used to characterize changes in cellulose nanopaper (NP) tensile properties. For the preparation of NP, high-purity cellulose from old, unused filter paper waste was used. Lignin and xylan were used as sustainable green interface engineering modifiers for NP due to their structural compatibility, low price, nontoxic nature, and abundance as a by-product of biomass processing, as well as their ability to protect cellulose fibers from UV irradiation. Nanofibrillated cellulose (NFC) suspension was obtained by microfluidizing cellulose suspension, and NP was produced by casting films from water suspensions. The use of filler from 1 to 30 wt% significantly altered NP properties. All nanopapers were tested for their sensitivity to water humidity, which reduced mechanical properties from 10 to 40% depending on the saturation level. Xylan addition showed a significant increase in the specific elastic modulus and specific strength by 1.4- and 2.8-fold, respectively. Xylan-containing NPs had remarkable resistance to UV irradiation, retaining 50 to 90% of their initial properties. Lignin-modified NPs resulted in a decreased mechanical performance due to the particle structure of the filler and the agglomeration process, but it was compensated by good property retention and enhanced elongation. The UV oxidation process of the NP interface was studied with UV-Vis and FTIR spectroscopy, which showed that the degradation of lignin and xylan preserves a cellulose fiber structure. Scanning electron microscopy images revealed the structural formation of the interface and supplemented understanding of UV aging impact on the surface and penetration depth in the cross-section. The ability to overcome premature aging in environmental factors can significantly benefit the wide adaption of NP in food packaging and functional applications.

Durability of Biodegradable Polymer Nanocomposites.

Biodegradable polymers (BP) are often regarded as the materials of the future, which address the rising environmental concerns. The advancement of biorefineries and sustainable technologies has yielded various BP with excellent properties comparable to commodity plastics. Water resistance, high dimensional stability, processability and excellent physicochemical properties limit the reviewed materials to biodegradable polyesters and modified compositions of starch and cellulose, both known for their abundance and relatively low price. The addition of different nanofillers and preparation of polymer nanocomposites can effectively improve BP with controlled functional properties and change the rate of degradation. The lack of data on the durability of biodegradable polymer nanocomposites (BPN) has been the motivation for the current review that summarizes recent literature data on environmental ageing of BPN and the role of nanofillers, their basic engineering properties and potential applications. Various durability tests discussed thermal ageing, photo-oxidative ageing, water absorption, hygrothermal ageing and creep testing. It was discussed that incorporating nanofillers into BP could attenuate the loss of mechanical properties and improve durability. Although, in the case of poor dispersion, the addition of the nanofillers can lead to even faster degradation, depending on the structural integrity and the state of interfacial adhesion. Selected models that describe the durability performance of BPN were considered in the review. These can be applied as a practical tool to design BPN with tailored property degradationand durability.

Cellulose Nanocrystals vs. Cellulose Nanofibers: A Comparative Study of Reinforcing Effects in UV-Cured Vegetable Oil Nanocomposites.

There is an opportunity to use nanocellulose as an efficient renewable reinforcing filler for polymer composites. There have been many investigations to prove the reinforcement concept of different nanocellulose sources for thermoplastic and thermoset polymers. The present comparative study highlighted the beneficial effects of selecting cellulose nanofibers (CNFs) and nanocrystals (CNCs) on the exploitation properties of vegetable oil-based thermoset composite materials-thermal, thermomechanical, and structural characteristics. The proposed UV-light-curable resin consists of an acrylated epoxidized soybean oil polymer matrix and two different nanocellulose reinforcements. High loadings of up to 30 wt% of CNFs and CNCs in irradiation-cured vegetable oil-based thermoset composites were reported. Infrared spectroscopy analysis indicated developed hydrogen-bonding interactions between the nanocellulose and polymer matrix. CNCs yielded a homogeneous nanocrystal dispersion, while CNFs revealed a nanofiber agglomeration in the polymer matrix, as shown by scanning electron microscopy. Thermal degradation showed that nanocellulose reduced the maximum degradation temperature by 5 °C for the 30 wt% CNC and CNF nanocomposites. Above the glass transition temperature at 80 °C, the storage modulus values increased 6-fold and 2-fold for the 30 wt% CNC and CNF nanocomposites, respectively. In addition, the achieved reinforcement efficiency factor r value for CNCs was 8.7, which was significantly higher than that of CNFs of 2.2. The obtained nanocomposites with enhanced properties show great potential for applications such as UV-light-processed coatings, adhesives, and additive manufacturing inks.

UV-Light Curing of 3D Printing Inks from Vegetable Oils for Stereolithography.

Typical resins for UV-assisted additive manufacturing (AM) are prepared from petroleum-based materials and therefore do not contribute to the growing AM industry trend of converting to sustainable bio-based materials. To satisfy society and industry's demand for sustainability, renewable feedstocks must be explored; unfortunately, there are not many options that are applicable to photopolymerization. Nevertheless, some vegetable oils can be modified to be suitable for UV-assisted AM technologies. In this work, extended study, through FTIR and photorheology measurements, of the UV-curing of epoxidized acrylate from soybean oil (AESO)-based formulations has been performed to better understand the photopolymerization process. The study demonstrates that the addition of appropriate functional comonomers like trimethylolpropane triacrylate (TMPTA) and the adjusting of the concentration of photoinitiator from 1% to 7% decrease the needed UV-irradiation time by up to 25%. Under optimized conditions, the optimal curing time was about 4 s, leading to a double bond conversion rate (DBC%) up to 80% and higher crosslinking density determined by the Flory-Rehner empirical approach. Thermal and mechanical properties were also investigated via TGA and DMA measurements that showed significant improvements of mechanical performances for all formulations. The properties were improved further upon the addition of the reactive diluents. After the thorough investigations, the prepared vegetable oil-based resin ink formulations containing reactive diluents were deemed suitable inks for UV-assisted AM, giving their appropriate viscosity. The validation was done by printing different objects with complex structures using a laser based stereolithography apparatus (SLA) printer.

Spent coffee waste as a renewable source for the production of sustainable poly(butylene succinate) biocomposites from a circular economy perspective.

Turning waste products into useable resources is a necessity for the sustainable future of our planet. Such is the case with popular beverage coffee that produces solid waste in the form of spent coffee grounds (SCG). There is an opportunity to use SCG material as a cheap, sustainable, and biodegradable polymer filler that is received as waste from espresso machines. There have been relatively many studies that prove the concept of various agricultural and forestry waste, which can be integrated into modern green materials. Building upon this concept, we have selected a promising polyester poly(butylene succinate) (PBS) as a matrix owing to its bio-based and biodegradable nature. High loadings of SCG from 20 to 60 wt% were tested for optimal composition performance. Tensile, dynamic mechanical, thermal, and structural properties of the composites were examined, while their biodegradation in composting conditions was also analyzed. SCG filler showed different performance from various cellulose fiber-based composites, and properties significantly varied depending on loading. Compared to neat PBS, biodegradation occurred twice as fast for composite materials with high SGC loadings.

Biorefinery Approach for Aerogels.

According to the International Energy Agency, biorefinery is "the sustainable processing of biomass into a spectrum of marketable bio-based products (chemicals, materials) and bioenergy (fuels, power, heat)". In this review, we survey how the biorefinery approach can be applied to highly porous and nanostructured materials, namely aerogels. Historically, aerogels were first developed using inorganic matter. Subsequently, synthetic polymers were also employed. At the beginning of the 21st century, new aerogels were created based on biomass. Which sources of biomass can be used to make aerogels and how? This review answers these questions, paying special attention to bio-aerogels' environmental and biomedical applications. The article is a result of fruitful exchanges in the frame of the European project COST Action "CA 18125 AERoGELS: Advanced Engineering and Research of aeroGels for Environment and Life Sciences".

Bio-Based Poly(butylene succinate)/Microcrystalline Cellulose/Nanofibrillated Cellulose-Based Sustainable Polymer Composites: Thermo-Mechanical and Biodegradation Studies.

Biodegradable polymer composites from renewable resources are the next-generation of wood-like materials and are crucial for the development of various industries to meet sustainability goals. Functional applications like packaging, medicine, automotive, construction and sustainable housing are just some that would greatly benefit. Some of the existing industries, like wood plastic composites, already encompass given examples but are dominated by fossil-based polymers that are unsustainable. Thus, there is a background to bring a new perspective approach for the combination of microcrystalline cellulose (MCC) and nanofibrillated cellulose (NFC) fillers in bio-based poly (butylene succinate) matrix (PBS). MCC, NFC and MCC/NFC filler total loading at 40 wt % was used to obtain more insights for wood-like composite applications. The ability to tailor the biodegradable characteristics and the mechanical properties of PBS composites is indispensable for extended applications. Five compositions have been prepared with MCC and NFC fillers using melt blending approach. Young's modulus in tensile test mode and storage modulus at 20 °C in thermo-mechanical analysis have increased about two-fold. Thermal degradation temperature was increased by approximately 60 °C compared to MCC and NFC. Additionally, to estimate the compatibility of the components and morphology of the composite's SEM analysis was performed for fractured surfaces. The contact angle measurements testified the developed matrix interphase. Differential scanning calorimetry evidenced the trans-crystallization of the polymer after filler incorporation; the crystallization temperature shifted to the higher temperature region. The MCC has a stronger effect on the crystallinity degree than NFC filler. PBS disintegrated under composting conditions in a period of 75 days. The NFC/MCC addition facilitated the specimens' decomposition rate up to 60 days.

Highly Loaded Cellulose/Poly (butylene succinate) Sustainable Composites for Woody-Like Advanced Materials Application.

We report the manufacturing and characterization of poly (butylene succinate) (PBS) and micro cellulose (MCC) woody-like composites. These composites can be applied as a sustainable woody-like composite alternative to conventional fossil polymer-based wood-plastic composites (WPC). The PBS/MCC composites were prepared by using a melt blending of 70 wt% of MCC processed from bleached softwood. MCC was modified to enhance dispersion and compatibility by way of carbodiimide (CDI), polyhydroxy amides (PHA), alkyl ester (EST), (3-Aminopropyl) trimethoxysilane (APTMS), maleic acid anhydride (MAH), and polymeric diphenylmethane diisocyanate (PMDI). The addition of filler into PBS led to a 4.5-fold improvement of Young's modulus E for the MCC composite, in comparison to neat PBS. The 1.6-fold increase of E was obtained for CDI modified composition in comparison to the unmodified MCC composite. At room temperature, the storage modulus E' was found to improve by almost 4-fold for the APTMS composite. The EST composite showed a pronounced enhancement in viscoelasticity properties due to the introduction of flexible long alkyl chains in comparison to other compositions. The glass transition temperature was directly affected by the composition and its value was -15 °C for PBS, -30 °C for EST, and -10 °C for MAH composites. FTIR indicated the generation of strong bonding between the polymer and cellulose components in the composite. Scanning electron microscopy analysis evidenced the agglomeration of the MCC in the PBS/MCC composites. PMDI, APTMS, and CDI composites were characterized by the uniform dispersion of MCC particles and a decrease of polymer crystallinity. MCC chemical modification induced the enhancement of the thermal stability of MCC composites.